Method of eliminating colloidal asphaltenes and carbenes from fuel oil



May 6, 1930. A. .JURRISSEN METHOD OF ELIMINATING COLLOIDAL ASPHALTENES AND CARBENES FROM FUEL OIL Filed Jan. 24, 1925 QQQSS Patented May v6, 1930 NrrED STA TES PATENT OFFICEA ALPHONSUS JLUBRISSEN, `OIE MARTINEZ, CALIFORNIA, ASSIGNOR T SIMPLEX BE- l 'IFINING COMPANY, A'CORPORATION Ol' CALIFORNIA METHOD 0F `EIIJINIINA.TINGr COLLOIDAL ASPHALTENES CARBENES FROM FUEL OIL y Application filed January y My invention relates to the art of oil refining. In 'that'art it is common practice to subj ect petroleum oils'and distillates to heat and pressure for the purpose of producing volatile or low boiling point hydrocarbons, such4 as 1o uid residuum consists ofhigh boilin materialvwhich is commonly used as fuel o1l.

gasoline, this operation` being commonly termed cracking, In Ythe cracking operation certain overhead distillates are pro-` duced, leaving a liquid residuum. This liqo' point but soluble in carbon-tetrachloride and ben,

zene. The carbenes are insoluble at atmospheric temperatures in petroleum-ether and 25 carbon-tetrachloride, but are soluble in benzene. The free carbon is, of course, insoluble at'all temperatures in -any ordinary solvent. There is no sharp line of demarcation between these three classes, some carbenes dllfering onlyslightly from free carbon and some as- 4 phaltenes being similar in properties to the carbenes. v

I have found that residuums roduced by crackin often contain all three c asses of substances ut that the proportion of each and the hysical properties of the residuums'so pro uced vary widely even in the operation of the same apparatus on the same oil.

The asphaltenes, carbenes and carbon are objectionable, since they tend to settle out of the oil, forming -V heavy adherent materlals which clog up the piping and burners ofthe fuel oil plants in which .they are used. So strong, in fact, is the pre]ud1oe agalnstthem thatit isl common practice to test fuel oils by centrifuging a mixture of equal vparts of benzol' and the oil to be tested, and such a test or# dinarily discloses largeamounts of asphaltenes, carbenes andcarbon in all cracked'residuums. l Some such residuums showing a vide apreheater v1,.a mixer Qr, apump 3,'a

24, 1925. Serial No. 4,537.

high proportion of 'colloidal and solidr matter,

while actually quite suitable for use as fuel oil, since the suspended matter does not readily settle out, are nevertheless unsalable due to the poor showing nlade when tested as above described. It is, therefore, of great importance to free the residuum from these suspended solids and colloids, and it is an obect of my invention to provide a means for so omg.

I have found that it is possible to remove the suspended free carbon by filtration, but if this carbon is associated or combined with colloidal'asphaltenes, and carbenes, it is not commercially feasible to operate filters lwhich quickly clog up dueto the accumulation of colloidal matter therein. It is a further object of myv invention to so treat acracked residuum that the colloids are physically changed into a form that will readily pass through a filter, which catches and removes the free carbon. Y

.I am now inclined to believe that the asphaltenes and carbenes vconsist of free carbon combined or associated with hydrocarbons,

and that due to the peculiar nature of the y combination the resulting substances are insoluble in the oil in which they are carried. l I havey found, however, that b treating these substances with powerful so vents, I can .apparently break the bond between the carbon and the hydrocarbon, and that, once this has be en done, the hydrocarbon goesreadily into solution in the original oil andpremains in sued 0e. 1

Iv have found that the asphaltenes and-caig-Y f benes, while apparently not `solublein the pe such solution even if the solventis then distroleum oil in which they are found, are nevertheless soluble in hot petroleum-ether, and

that afterthe evaporation of the petroleumether there is left a substance almost completely soluble in the original oil.

Further objects and advantages 'will bev `madeevident hereinafter. v The annexed drawing shows diagrammati- (muy Partly in SBCQD 9111 apparatus forpracticing my invention. In this drawing I pro..

'still 4,.a vapor separator 5, a filter 6, and a condenser 7.

1 When operating my 'invention directly in connection with a cracking plant, it is unnecessary to rovide the preheater 1, the hot residuum eing delivered directly into the mixer 2 from the cracking still. Where it is desired to treat/cold fuel oil orresiduum, the preheater 1 is provided and it may consist of a coil 11 of any convenient form heated by a burner 12, the heated oil being delivered through a pipe 13 into'the mixer 2.

The mixer 2 consists of a tight shell 20 having a coned bottom terminating in a dumping pipe *21, normally closed by a Valve 22-and used only to clean the mixer at long intervals. Mounted on a shaft 23 inside the shell 20 is a plurality-of paddles 24, the shaft 23 extending upwardly through the top of the shell and being provided with a pulley 25 which may be drlven from any suitable source of power (not shown). A solvent inlet pipe 26, having a Valve 27, delivers solvent from a suitable storage tank 28 into the mixer 2. Fluid is delivered from near the top of the mixer 2 through a pipe 29 to the pump 3.

' The pump 3 may be of any convenient Yi'orm andv it delivers liquid through a pipe 31 to the I stil14. f

The still 4 maybe of the form shown, consisting of a plurality of tubes 41 passing through a furnace 42 heated by any convenient means, such as the oil or gas burner 43. Fluid is delivered from the still4'through a pipe 44 to a ring of pipe 45 having perforaf tions therein situated in the top of the vapor separator 5.

The vapor separator 5 consists of a tight shell 51 having a central vapor outlet pipe 52.

Carried on the pipe 52 within the shell 51 is a l plurality of spreader cones 53. The lower end of the pipe 52 is open and perforations 54 are provided in the pipe 52 between the cones 53. Vapor is taken olf through the pipe 52 and liquid is delivered through a pipe 55 tothe filter 6.

The filter 6 may be of any convenient form and serves to separate solid material from' the oil delivered through the pipe 55, cleaned Y oil being delivered through a pipe 61 to spuitable storage.,

connects with a pipe 57 having a valve58.

.Vapor is delivered by the pipe 52 into the' condenser 7 which maybe of any convenient form, that shown consisting lof a tight sheel 7ll vhaving intermediate heads 72, between which tubes 73 extend. Vapors pass through the tubes 73, the space aroundv the tubes7 3,

` between the heads 72, being filled with cool'- ing I water delivered by a pipe 74, heated water being taken off. by a pipe 75. The con-v densates 'from the condenser -7 are delivered by 'a pipe intol the mixer 2.

A convenient method of operating my invention is as follows:

The mixer 2 being partially filled with solvent rom the tank 28 through the pipe 26, hot residuum from the cracking still (not shown), or from the preheater 1, is run into the mixer 2 through the pipe 13. The residuum and solventy are thoroughly mixed by the paddles 24 and the mixture is-delivered by the pipe 29 t-o the pump 3 and forced 'by the pump 3 into the still 4.

In practice I may use anyl suitable solvent, such as carbon-tetrachloride, petroleum-ether or other petroleum distillate. In practice I preferto maintain the mixer 2 at a temperature below the boiling point of the solvent. In the still 4 I heat the mixture delivered thereto by the pipe 31 to such a temperature that all the solvent is vaporized, the pipes 44 and 45 delivering the mixture in the form of foam into the top of the vapor separator` 5. This foam is spread by the upper cone 53, passing downwardly along the inner wall of the shell 51. Duri-ng its downward passage., the solvent is vaporized, passing upwardly A throughthe pipe 52 to the condenser 7, where it is condensed, being then delivered as a hot l the mixer 2, so that very little solvent need be supplied from the solvent tank 28 during the operation of my invention. w `The separated residuum is delivered from the separator v5 through the pipe'55 to the filter 6, or throughthe pipe 57 to suitable storage.

The oil delivered through the pipe 57 is substantially free from colloidal asphaltenes or carbenes, and the free carbon is in such form thatit can be readily liltered out in the ilter 6, so that the oil delivered through the pipe 61 is substantially l:free from colloidal asphaltenes and carbenes, and free carbon.

'I am inclined to `think that the asphaltenes and carbenes are in reality colloidal combinations ofcarbon and hydrocarbons..

While I do not wish'4 to be understood as' definitely committing myself asl to any theory of the operation of my invention, Ibev The pipe 55 is Provided with a Valve 56 and lieve the following is a probable one.

My invention probably depends upon the fact that the Aasphaltenesand carbenes, while insoluble. in cold petroleum of high boiling point, are readily dissolved in hotetroleum the asphaltenesand carbenes by hot solvents;

and when so dissolved, to dissolve them in the oil in which they were previously suspended. f

`Il'oids is dissolved, perhaps first in the solvent and then inthe petroleum, so that upon the v removal of the solvent by heat the soluble and solid material lin one particular sample portion of the colloid is left in solution in the Vpetroleum and theinsoluble portion ap` pears as free suspended carbon.

Whatever may be the theory of operation I have found that by treating cracked residuums as described, some very remarkable results are produced. f v

For example, I have found that some residuums show as high as 32 per cent ofv colloidall and solid material when centrifuged with an equal part of benzol. This colloidal showed about 12 per 'cent coke when extracted with benzol. Other samples of the same material'were found to contain 87.4 er cent of matter soluble in carbon-tetrachloride, 86.4 per cent of matter soluble in benzene, and 69.5 per cent of matter soluble in petroleumether. By treating this particular 'residu- A um, which initially contained 32 per cent ofcolloidal 'and solid mat-ter, with carbon-tet- `ra'chloride, which was then distilled off, I produced an oil containing les's than 6 per cent of colloidal and solid matter which was in such a condition as to readily filter out.

are

This is not an exceptional case andin fact I have been able in some casesfby the use of my invention, treating a residuum containing 30 per cent of colloidal and solid matter, to reduce this matter to less than 2 per cent without filtration. Such a product is 'commercially satisfactory without filtration.I

I have also found that comparatively small proportions of solvent are sufficient in lmany cases, the mixture delivered to the still lcon'- taining less than 20 per cent of solvent.

I have also found that although carbontetrachloride and other relatively expensive v solvents give superior results, it is commercially feasible to operate using as solvents the lighter petroleum distillates 'produced commercially in large quantities 1n many large oil refineries.

By my invention I amable'to very cheaply treat what are now regarded as most undesirable residues to produce `acceptable fuel oils. In so doing I dol not d it necessary to reduce the bulk ofthe oil b -entirely re-- matter carv ried therein, ybut onthe contrary I merge moving the colloidal and soli the larger part of this matter into-the/'fuel oil itself. .My process therefore, superior to any filtration process in which all the asphaltenes andearbenes mightl be removed,`

in that it converts-the useless substances into v`My invention also has a special utility in` that it is particularly well suited to handle oils vhaving a relatively low free carbon content but containing alarge proportion of asphaltenes and carbenes. Previousl to my invention such oils were substantially useless even as fuel'oils.v No method was known of treating them to remove the asphaltenes and carbenes, which could not be successfully filtered out due lto their viscous or colloidal nature and `which settled out very slowly if allowed to stand. Such loils which showed perhaps as high as 30 per cent 'of colloidal and solid matter were', therefore, not salable in their original form due to their sludge test, and could not be successfully treated to makethem salable. By my invention such oils can generally be so treated as-to be readily salable and in many cases this can be accomplished without filtration.

I claim as my invention: i

1. A recess of treating cracking residues of petro eum oils, containing particles of substantially free carbon, which tend to adsorb liquid hydrocarbons in the nature of colloidal asphaltenes-and carbenes, and to settle out'from the residuein the form of sludge, for the purpose of reducing the quantity of material so adsorbed or liable to be adsorbed, comprising: adding to the cracking residue a sufficient 'quantity of a lighter petroleum distillate capable of dissolving asphaltenes and carbenes, mixing both materials and keeping the mixture at an 'elevatedtemperature, not over the boiling point of the lighter petroleum distillate, fora suilieient time to remove most of the asphaltenes and carbenes v from the free carbon, dissolving them in the balance of the cracking residue, and removing the mixture'tostorage.

` 2'. A process of treating cracking residues o f petroleum oils, containing particles of substantially free carbon, which tend to adsorb liquid hydrocarbons in the nature of coloidal asphaltenes and carbenes, and `to ilo settle outfrom the residue inthe form ofsludge,g for the purpose of reducing the uantity of material so adsorbed or liablegto be r adsorbed, comprising-z adding to the crack ling residue a sulcient quantity o f alighter petroleum distillate obtainedfrom a cracking process, vandcapable of dissolving as-v ,'phaltenes and carbenes, mixing both -1`na- .terials r and keeping the mixture at if elevated temperature, notI over the boiling .point of the 'lighter petroleum distillate, yfor a sufficient 'time to remove most of the asphaltenes and. carbenes from the free carbon, dissolving themY in the balance of the ESO cracking residue, and removing the mixture to storage. y

' 3. A. Jprocess of treating cracking residues' of petroleum oils, containingl particles of substantially free carbon, which tend to adsorb liquid hydrocarbons in the nature of colloidal asphaltenes and carbenes, and to settle out from the residue in the form vof sludge, for the purpose of reducing the quantity of material so adsorbed or liable tobe adsorbed, comprising: adding to the cracking ,residue av suiicient quantity of a lighter petroleum distillate capable of dissolving asphaltenes and carbenes, mixing both materials and keeping the mixture at an elevated temperatura not over the boiling point of the", lighter petroleum distillate, for a suliiil cieI'lttime-to remove most of the asphaltenes stantially free carbon, Which tend to adsorb liquid hydrocarbons in the nature of colloidal asphaltenes and carbenes, and to settle out from the residue in the form of sludge, for the purpose of reducing the quantity'of ma- Y .terial so adsorbed" or liable to be adsorbed,

comprising: adding to the cracking residue a sufficient quantity of petroleum ether capable of dissolving asphaltenes and carbenes, mixing both materials and keeping the mixture at an elevated temperature, not over the boilmg point of the petroleum ether, for a suii-K' cient time to remove most of the asphaltenes and carbenes .from the free carbon, dissolvmg them 1n the .balanceof the cracking resii due, and removin the mixture to storage.

' 5. A process o treating cracking residues of petroleum oils, containing particles of sorb liquid hydrocarbons in the ,nature of colloidal asphaltenes and carbenes, and to settle out from the residue in the form of sludge, for the purpose of reducing the quantity of materialv so adsorbed or liable to be adsorbed, comprising: adding to the cracking residue a suicient quantity of a lighter petroleum distillate capable of dissolving asphaltenes and carbenes, mixing both materials and keeping the mixture at an elevated temperature, not over the boiling point of the lighter petroleum distillate, for a sufficient time to remove most of the asphaltenes and carbenes from the free carbon, dissolving them in the balance of the cracking residue, distilling off the lighter petroleum distillate,

condensing and returning this distillate for reuse to the mixing chamber, filtering olf from the residue substantially only the solid granular carbon material," and removing the residue to storage.

In'testimony whereof, I have hereunto set my hand at Martinez, California, lthis 14th day of January, 1925. l

c ALPHONSUS JURRISSEN.

substantially free carbon, which tend to ady sorbliquidhydrocarbons in the'nature of colloidal asphaltenes and carbenes, and .to settle out from the residue in the form of'sludge.

. for the, urpose of reducing the quantity o vmateria so adsorbed or liable to be adsorbed,

al slcient quantity of a li hter petroleum distillate capablev of dissolving asphaltenes and carbenes, mixing both materials and keeping the mixture at an elevated temperature, not overthe boilin point of the ighter petroleum distillate, or a suicient' time to remove most of `the asphaltenes and onlythe solid granular carbon material,`"and carbenes from thev free carbon, dissolving them in the balance ofthe crackingresidue,

distilling olf the lighter petroleum distillate,

filtering olf fromthe `residue, substantially of petroleum `oi1s,j contaming'particles of c substantially free carbon, which tend to ad- 

